CN106995444B - A kind of loop coil bisglyoxaline molecule, preparation method and application - Google Patents
A kind of loop coil bisglyoxaline molecule, preparation method and application Download PDFInfo
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- CN106995444B CN106995444B CN201710190337.7A CN201710190337A CN106995444B CN 106995444 B CN106995444 B CN 106995444B CN 201710190337 A CN201710190337 A CN 201710190337A CN 106995444 B CN106995444 B CN 106995444B
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Abstract
The invention patent discloses a kind of bisglyoxaline molecule of New-type spiro structure and the preparation method and application of related derivatives.Using benzophenone or and its derivative as raw material, by Corey-Fuchs reaction its corresponding dibromo aromatic ring olefin product is prepared；Then Suzuki occurs with o- formaldehyde phenyl boric acid to react, obtains replacing four aryl ethylenes together with position-ortho position aldehyde radical；Again with benzil or and its derivative Leuckart occurs in acetic acid, ammonium acetate and reacts to obtain together with position-ortho position tetraphenylethylene-triphenylimidazolyl；Finally in K3Fe(CN)6Under the oxidation of/KOH, the loop coil bisglyoxaline molecule is obtained by free radical cycloaddition.This kind of molecules at low temperature (77K) show longer life (1.6 seconds) phosphorescence luminescent behavior.This kind of 3D helical molecules are possible to prepare the room temperature phosphorimetry organic small molecule material of long-life and provide guidance.
Description
Technical field
The invention belongs to organic synthesis fields, more particularly, to a kind of New-type spiro bisglyoxaline small organic molecule, its conjunction
At method and application.
Background technique
Organic photochromic material is many kinds of, including with bisglyoxaline (hexaarylbiimidazole, abbreviation
HABI) the novel molecular switch generated free radicals for the illumination of parent.Traditional bisglyoxaline MOLECULE DESIGN, due to two points after illumination
Sub- imidazole radical is separated from each other, and is faded slow, anti-fatigue performance is poor, can not practical application.In recent years, it was set using bridging molecules
Count the modified bisglyoxaline molecule of obtained intramolecular bridging be proved to have be exceedingly fast fade rates (J.Am.Chem.Soc.2004,
126,6526-6527；J.Am.Chem.Soc.2009 131,4227–4229；J.Am.Chem.Soc.2014,136,3796-
3799；) and unusual negative photochromic effect J.Am.Chem.Soc.2015,137,4952-4955
(J.Am.Chem.Soc.2013,135,3164-3172) causes the great interest of researcher immediately.And tetraphenylethylene
(tetraphenylethene, abbreviation TPE) is as aggregation-induced emission (Aggregation InducedEmission, abbreviation
AIE star molecule) become the research of current solid luminescent hot topic (J.Mater.Chem., 2012,22,23726；
Chem.Soc.Rev.,2011,40,5361；Chem.Rev., 2015,115,11718).Accordingly, assembled using tetraphenylethylene
The intramolecular bridging of the characteristics of induced luminescence and bisglyoxaline design, be hopeful to obtain be provided simultaneously with quickly colour fading, aggregation inducing
Luminous role in fluorescent molecule switch is hopeful to apply to super-resolution imaging field.On the other hand, based on bisglyoxaline it is photochromic with
And fluorescent switch material is reported successively, however up to the present, have the luminous bisglyoxaline molecule of long lifetime phosphorescent but
Do not report.Therefore, exploitation has the luminous molecular switch of phosphorescence and is hopeful to obtain new breakthrough in phosphorescent molecules field of switches.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of loop coil bisglyoxaline molecules, its conjunction
At method and application, its object is to by being prepared a kind of novel with loop coil knot together with position cross-coupling synthesizing mean
The bisglyoxaline small organic molecule of structure has very long phosphorescence lighting time interval at low temperature, is applied to the luminous material of phosphorescence
Thus material solves the technical issues of prior art lacks phosphorescence luminous bisglyoxaline molecule.
To achieve the above object, according to one aspect of the present invention, a kind of loop coil bisglyoxaline molecule, the loop coil are provided
Bisglyoxaline molecule has the molecular structural formula as shown in formula (one)
Wherein, X H, O, S, SO2Or Se；R1For H, F, Cl, Br, I, N (CH3)2Or O (CH2)nCH3；R2For H, F, Cl, N
(CH3)2Or O (CH2)nCH3, n be 0~7 integer.
Preferably, the X is H, S or O, R1For H or OCH3, R2For H, OCH3, F or Cl.
Preferably, the loop coil bisglyoxaline molecule, when temperature is 77K, phosphorescence fluorescent lifetime is up to 1.6 seconds.
Other side according to the invention provides a kind of preparation method of loop coil bisglyoxaline molecule, with benzophenone
Or and its derivative be raw material, by Corey-Fuchs reaction its corresponding dibromo aromatic ring olefin product is prepared；Then
Suzuki occurs with o- formaldehyde phenyl boric acid to react, obtains replacing four aryl ethylenes together with position-ortho position aldehyde radical；Again with benzil or
And its Leuckart occurs in acetic acid, ammonium acetate and reacts to obtain together with position-ortho position tetraphenylethylene-triphenylimidazolyl for derivative；
Finally in K3Fe(CN)6Under the oxidation of/KOH, the loop coil bisglyoxaline molecule is obtained by free radical cycloaddition.
Preferably, the preparation method of the loop coil bisglyoxaline molecule, includes the following steps:
(1) diaryl ketone and carbon tetrabromide, triphenylphosphine are dissolved in toluene according to molar ratio 1:2~4:4~8,
It is heated to 100~140 DEG C to flow back 1~4 day, after fully reacting, is spin-dried for solvent, residue is separated using silica gel column chromatography,
Then the product being collected into is obtained into 1,1 '-two bromo- 2,2 '-diarylethenes with ethyl alcohol recrystallization；
(2) 1,1 '-the two bromo- 2,2 '-diarylethenes for obtaining step (1) and adjacent benzaldehyde phenyl boric acid, potassium carbonate with
And zero valent palladium catalyst is dissolved in the mixed solution of toluene and water according to molar ratio 1:2~4:4~8:0.05~0.1,90
Under the conditions of~110 DEG C, is reacted 12~24 hours under nitrogen atmosphere, after fully reacting, water phase is extracted with dichloromethane, is associated with
Machine phase, is then spin-dried for solvent, and obtained residue is isolated and purified on silica gel column chromatography and obtains 2,2 '-diaryl-hexichol
Formaldehyde；
(3)-two benzaldehyde of 2,2 '-diaryl that step (2) is prepared and benzil, ammonium acetate are according to molar ratio 1:
2~4:10~30 are dissolved in acetic acid, are heated to 70~100 DEG C, are stirred to react 24~48 hours, to the end of reacting after, will
Reaction solution is added dropwise in saturated salt solution dropwise, and white precipitate is collected by filtration, and is washed, dry, then by residue in silicagel column
It is purified on chromatography, obtains-two triphenylimidazolyl of 2,2 '-diaryl；
(4) iron blood salt and potassium hydroxide are dissolved in deionized water, are added dropwise to step (3) is prepared 2,2 '-two
In-two triphenylimidazolyl of aryl, described 2 ,-two triphenylimidazolyl of 2 '-diaryl is dissolved in methylene chloride, the iron blood salt,
Potassium hydroxide and 2, the molar ratio of-two triphenylimidazolyl of 2 '-diaryl are 10~20:20~50:1, and it is small to stir 2~12 at room temperature
When, after fully reacting, upper strata aqueous phase is extracted with dichloromethane, merges organic phase, it is dry, it is spin-dried for solvent, then by residue
In silica gel, successively upper purifying obtains the loop coil bisglyoxaline molecule.
Other side according to the invention provides the application of loop coil bisglyoxaline molecule described in one kind, is applied to system
Standby phosphorescent light-emitting materials.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
1) New-type spiro bisglyoxaline molecule of the invention is the small organic molecule of a kind of long lifetime phosphorescent emitting performance；
2) bisglyoxaline has the fade rates being exceedingly fast, and new loop coil bisglyoxaline molecule proposed by the present invention can be quickly colour fading
Photochromic material new selection is provided；
3) present invention by benzophenone compound by Corey-Fuchs and Suzuki-Coupling react to obtain together with
Four aryl ethylene neighbour's dialdehyde of position-ortho position substitution；It reacts to obtain with benzil (and its derivative) under acetic acid, ammonium acetate medium
Four aryl ethylene triphenylimidazolyls；Then, iron blood salt, potassium hydroxide aqueous solution in be oxidized, occur freely it is cyclization plus
At passing through each step by controlling each step reaction condition and parameter (such as type and proportion of reactant, temperature, time etc.)
A kind of novel bisglyoxaline small organic molecule with spirane structure is prepared, at low temperature in overall co-ordination between rapid
(77K) shows the phosphorescence luminescent behavior of longer life, so as to develop long-time room temperature phosphorimetry based on such molecule
Material solves the technical issues of prior art lacks phosphorescence luminous bisglyoxaline molecule.
Detailed description of the invention
Fig. 1 is the synthetic route chart of the loop coil bisglyoxaline molecule of the embodiment of the present invention 1；
Fig. 2 is the hydrogen spectrum of the loop coil bisglyoxaline molecule of the embodiment of the present invention 1；
Fig. 3 is the carbon spectrum of the loop coil bisglyoxaline molecule of the embodiment of the present invention 1；
Fig. 4 is the mass spectrum of the loop coil bisglyoxaline molecule of the embodiment of the present invention 1；
Fig. 5 is the single crystal diffraction of the loop coil bisglyoxaline molecule of the embodiment of the present invention 1；
Fig. 6 is the loop coil bisglyoxaline molecule absorption in solution, fluorescent emission and low at room temperature of the embodiment of the present invention 1
Phosphorescent emissions (a) and phosphorescent lifetime (b) under temperature；
Fig. 7 is 4,4 '-methoxyl groups-thioxanthones-loop coil bisglyoxaline molecule synthetic route chart of the embodiment of the present invention 2；
Fig. 8 is the chloro- thioxanthones of 4,4 '-methoxyl group-two-loop coil bisglyoxaline molecule synthetic route of the embodiment of the present invention 3
Figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of loop coil bisglyoxaline molecules, have following structural formula:
Wherein, X H, O, S, SO2Or Se, preferably H, S or O；R1For H, F, Cl, Br, I, N (CH3)2Or O (CH2)nCH3,
Preferably H or OCH3；R2For H, F, Cl, N (CH3)2Or O (CH2)nCH3, preferably H, OCH3, F or Cl；Wherein, n is 0~7
Integer.
The loop coil bisglyoxaline molecule shows the phosphorescence luminescent behavior of longlife noodles at low temperature, for example it is 77K in temperature
When phosphorescence fluorescent lifetime be up to 1.6 seconds (τp=1.6s).
The loop coil bisglyoxaline molecule can be obtained by following synthesis thinking: with benzophenone or and its be derived) it is original
Its corresponding dibromo aromatic ring olefin product is prepared by Corey-Fuchs reaction in material；Then it is sent out with o- formaldehyde phenyl boric acid
Raw Suzuki reaction, obtains replacing four aryl ethylenes together with position-ortho position aldehyde radical；Again with benzil or and its derivative acetic acid,
Leuckart occurs in ammonium acetate to react to obtain together with position-ortho position tetraphenylethylene-triphenylimidazolyl；Finally in K3Fe(CN)6/KOH
Oxidation under, obtain the loop coil bisglyoxaline molecule by free radical cycloaddition.
Specifically, the preparation method of such loop coil bisglyoxaline molecule, includes the following steps:
(1) diaryl ketone and carbon tetrabromide, triphenylphosphine are dissolved in toluene according to molar ratio 1:2~4:4~8,
It is heated to 100~140 DEG C to flow back 1~4 day, after fully reacting, is spin-dried for solvent, residue is separated using silica gel column chromatography,
Then the product being collected into is obtained into 1,1 '-two bromo- 2,2 '-diarylethenes with ethyl alcohol recrystallization；
(2) 1,1 '-the two bromo- 2,2 '-diarylethenes for obtaining step (1) and adjacent benzaldehyde phenyl boric acid, potassium carbonate with
And zero valent palladium catalyst is dissolved in the mixed solution of toluene and water according to molar ratio 1:2~4:4~8:0.05~0.1,90
Under the conditions of~110 DEG C, is reacted 12~24 hours under nitrogen atmosphere, after fully reacting, water phase is extracted with dichloromethane, is associated with
Machine phase, is then spin-dried for solvent, and obtained residue is isolated and purified on silica gel column chromatography and obtains 2,2 '-diaryl-hexichol
Formaldehyde；
(3)-two benzaldehyde of 2,2 '-diaryl that step (2) is prepared and benzil, ammonium acetate are according to molar ratio 1:
2~4:10~30 are dissolved in acetic acid, are heated to 70~100 DEG C, are stirred to react 24~48 hours, to the end of reacting after, will
Reaction solution is added dropwise in saturated salt solution dropwise, and white precipitate is collected by filtration, and is washed, dry, then by residue in silicagel column
It is purified on chromatography, obtains-two triphenylimidazolyl of 2,2 '-diaryl；
(4) iron blood salt and potassium hydroxide are dissolved in deionized water, are added dropwise to step (3) is prepared 2,2 '-two
In-two triphenylimidazolyl of aryl, described 2 ,-two triphenylimidazolyl of 2 '-diaryl is dissolved in methylene chloride, iron blood salt, hydrogen-oxygen
Change potassium and 2, the molar ratio of-two triphenylimidazolyl of 2 '-diaryl is 10~20:20~50:1, it is described be added dropwise after room temperature
After fully reacting, upper strata aqueous phase is extracted with dichloromethane in lower stirring 2~12 hours, merges organic phase, dry, is spin-dried for solvent,
Then by residue, in silica gel, successively upper purifying obtains the loop coil bisglyoxaline molecule.
Remaining analog can obtain target product according to this synthetic route.
The loop coil bisglyoxaline molecule that the present invention is prepared, since (77K) shows the phosphorescence hair of longer life at low temperature
Light behavior develops long-time room temperature phosphorimetry material based on such molecule, solves the prior art and lacks the luminous connection of phosphorescence
The technical issues of imidazole molecule, while also laying the foundation to develop a kind of novel aggregation-induced emission role in fluorescent molecule switch.
The following are embodiments:
Example 1
X, R in formula (one)1And R2H when being, the loop coil bisglyoxaline molecule are benzophenone-loop coil bisglyoxaline molecule,
It includes following four synthesis step that it, which is synthesized, as shown in Figure 1:
1) preparation of 1,1 '-two bromo- 2,2 '-diphenylethlenes
In 500ml single necked round bottom flask, by benzophenone (3.04g, 16,68mmol) and carbon tetrabromide (11.06g,
33.36mmol), triphenylphosphine (17.53g, 66.84mmol) etc. is dissolved in toluene (250ml), is heated to 140 DEG C of reflux 4
It.After fully reacting, it is spin-dried for solvent, residue is adopted into silica gel and is used column chromatography, the product ethyl alcohol that then will be collected into
It is recrystallized to give 4.91g white crystal, yield 87.1%.Target molecule 1,1 '-two bromo- 2 can be obtained by following general formula,
2 '-diphenylethlenes
2) synthesis of-two benzaldehyde of 2,2 '-diphenyl
In the twoport flask of 250ml, by 1,1 '-two bromo- 2,2 '-diphenylethlenes (1g, 2.95mmol) and adjacent benzene first
Aldehyde phenyl boric acid (1.33g, 8.88mmol), potassium carbonate (1.64g, 11.88mmol) and zero valent palladium catalyst (0.34g,
It 0.3mmol) is dissolved in the mixed solution of toluene (80ml) and water (40ml), under the conditions of 90 DEG C, reacts 12 under nitrogen atmosphere
Hour.After reaction terminates, water phase is extracted with dichloromethane, merges organic phase, is then spin-dried for solvent.Obtained residue is existed
It is isolated and purified on silica gel column chromatography and obtains target product compound a, 0.21g white powder, yield 18%.Press following general formula
Target product can be obtained
3) synthesis of-two triphenylimidazolyl of 2,2 '-diphenyl
In the twoport flask of 10ml, by compound a (0.3g, 0.77mmol), benzil (0.65g, 3.1mmol) and second
Sour ammonium (1.79g, 23.22mmol) is dissolved in acetic acid (1ml).Reactant is stirred to react one day under the conditions of being heated to 90 DEG C.
After to the end of reacting, reaction solution is added dropwise in saturated salt solution dropwise, white precipitate is collected by filtration, washed, it is dry.Then
Residue is purified on silica gel column chromatography, obtains pale yellow powder 0.29g compound b, yield 49%.
4) synthesis of benzophenone loop coil bisglyoxaline
In the twoport round-bottomed flask (100ml) equipped with constant pressure funnel, addition compound b (0.2g,
It 0.26mmol) is then dissolved in 40ml methylene chloride.By iron blood salt (1.71g, 5.19mmol) and potassium hydroxide (0.72g,
It 12.9mmol) is dissolved in 40ml deionized water, then in careful addition constant pressure funnel.It is hidden on twoport round-bottomed flask
Iron blood saline solution is added dropwise dropwise, is vigorously stirred at room temperature 2 hours for lid masking foil shading.After fully reacting, methylene chloride is used
Upper strata aqueous phase is extracted, organic phase is merged, it is dry, it is spin-dried for solvent.Then residue target is obtained in silica gel successively upper purifying to produce
Object, 0.18g, 90%.Reacted according to following general formula.
Fig. 2 and Fig. 3 is the hydrogen spectrum and carbon spectrum for the loop coil bisglyoxaline molecule that the present embodiment is prepared respectively；Fig. 4 is the spiral shell
The mass spectrum of ring bisglyoxaline molecule；Fig. 2 hydrogen spectrum shows the miaow for being located at low field (chemical displacement value 12.6) in loop coil bisglyoxaline molecule
Azoles NH disappears after oxidation；And carbon spectrum shows loop coil bisglyoxaline there is sp3The carbon atom (77.51 and 78.86) of hydridization；Fig. 4
The molecular mass for showing loop coil bisglyoxaline is 767.337 and molecular formula C56H38N4It matches；
Fig. 5 is the single crystal diffraction of the loop coil bisglyoxaline molecule；The space that Fig. 4 then directly demonstrates loop coil bisglyoxaline is absolute
Configuration: i.e. two molecule imidazole radical attack ethylene double bonds occur addition reaction and obtain five-membered ring and the alternate space of hexatomic ring
3D configuration；
Fig. 6 is the phosphorescence hair under absorption, fluorescent emission and low temperature of the loop coil bisglyoxaline molecule at room temperature in solution
Penetrate (a) and phosphorescent lifetime (b).It can be seen that the maximum absorption band of loop coil bisglyoxaline in 320nm from Fig. 6 a, fluorescence emission peak exists
390nm and phosphorescent emissions peak are 510nm；Its available phosphorescent lifetime of Fig. 6 b is 1.6s.
Embodiment 2
Work as X=S, R1=OCH3, R2When=H, the synthesis of thioxanthones-loop coil bisglyoxaline includes following four synthesis step
It is rapid: if Fig. 7, Fig. 7 are 4,4 '-methoxyl groups-thioxanthones-loop coil bisglyoxaline molecule synthetic route chart；
1) preparation of thioxanthones dibromoethylene
In 500ml single necked round bottom flask, by thioxanthones (3.00g, 14.15mmol) and carbon tetrabromide (13.91g,
42.45mmol), triphenylphosphine (22.25g, 84.9mmol) etc. is dissolved in toluene (250ml), is heated to 140 DEG C and is flowed back 2 days.
After fully reacting, it is spin-dried for solvent, residue is adopted into silica gel and is used column chromatography, then ties the product being collected into again with ethyl alcohol
Crystalline substance obtains 3.80g white crystal, yield 73.4%.The bromo- 2,2 '-thiophene of target molecule 1,1 '-two can be obtained by following general formula
Ton ketone ethylene
2) synthesis of two benzaldehyde of thioxanthones-(neighbour)
In the twoport flask of 250ml, by thioxanthones dibromoethylene (3.65g, 10.00mmol) and adjacent benzaldehyde phenyl boric acid
(4.50g, 30.00mmol), potassium carbonate (8.29g, 60.00mmol) and zero valent palladium catalyst (1.15g, 1mmol) are dissolved in
In the mixed solution of toluene (80ml) and water (40ml), under the conditions of 90 DEG C, reacted 24 hours under nitrogen atmosphere.React end
Afterwards, water phase is extracted with dichloromethane, merges organic phase, is then spin-dried for solvent.Obtained residue is divided on silica gel column chromatography
Target product, 1.52g white powder, yield 36.4% are obtained from purifying.Target product can be obtained by following general formula
3) thioxanthones-triphenylimidazolyl preparation
In the twoport flask of 25ml, by two benzaldehyde (0.42g, 1mmol) of thioxanthones-(neighbour), 4,4 '-dimethoxys-
Benzil (0.68g, 2.5mmol) and ammonium acetate (1.93g, 25mmol) are dissolved in acetic acid (8ml).Reactant is being heated to
Under the conditions of 100 DEG C, it is stirred to react one day.After to the end of reacting, reaction solution is added dropwise in saturated salt solution dropwise, filtering is received
Collect white precipitate, washes, it is dry.Then residue is purified on silica gel column chromatography, obtains pale yellow powder 0.73g, yield
79.3%.
4) thioxanthones-loop coil bisglyoxaline synthesis
In the twoport round-bottomed flask (100ml) equipped with constant pressure funnel, thioxanthones-triphenylimidazolyl is added
(0.4g, 0.44mmol) is then dissolved in 40ml methylene chloride.By iron blood salt (2.90g, 8.88mmol) and potassium hydroxide
(1.23g, 22mmol) is dissolved in 40ml deionized water, then in careful addition constant pressure funnel.It is burnt in twoport round bottom
Masking foil shading is covered on bottle, and iron blood saline solution is added dropwise dropwise, is vigorously stirred at room temperature 8 hours.After fully reacting, with two
Chloromethanes extracts upper strata aqueous phase, merges organic phase, dry, is spin-dried for solvent.Then by residue, in silica gel, successively upper purifying is obtained
Target product, 0.32g, 80%.Reacted according to following general formula.
Embodiment 3
Fig. 8 is the chloro- thioxanthones of 4,4 '-methoxyl group-two-loop coil bisglyoxaline molecule synthetic route chart, and such as Fig. 8 works as X=H,
R1=OCH3, R2When=Cl, the synthesis of thioxanthones-loop coil bisglyoxaline includes following four synthesis step:
1) preparation of 4,4 '-dichlorophenyl dibromoalkenes
In 500ml single necked round bottom flask, by 4,4 '-two chloro- benzophenone (2.50g, 10.00mmol) and carbon tetrabromide
(13.10g, 40.00mmol), triphenylphosphine (20.97g, 80.00mmol) etc. are dissolved in toluene (250ml), are heated to 140
DEG C reflux 3 days.After fully reacting, it is spin-dried for solvent, residue is adopted into silica gel and is used column chromatography, the product that then will be collected into
2.85g white crystal, yield 70.5% are obtained with ethyl alcohol recrystallization.Target molecule 1,1 '-two can be obtained by following general formula
Bromo- 4,4 '-dichlorophenyl ethylene
2) synthesis of 4,4 '-two chloro- (neighbour) two benzaldehydes
In the twoport flask of 250ml, by 1,1 '-two bromo- 2,2 '-diphenylethlenes (4.03g, 10.00mmol) and adjacent
Benzaldehyde phenyl boric acid (6.00g, 40.00mmol), potassium carbonate (11.06g, 80.00mmol) and zero valent palladium catalyst (0.58g,
It 0.5mmol) is dissolved in the mixed solution of toluene (120ml) and water (60ml), under the conditions of 90 DEG C, reacts 24 under nitrogen atmosphere
Hour.After reaction terminates, water phase is extracted with dichloromethane, merges organic phase, is then spin-dried for solvent.Obtained residue is existed
It is isolated and purified on silica gel column chromatography and obtains target product, 1.12g white powder, yield 24.6%.Press following general formula
Obtain target product
3) synthesis of 4,4 '-two chloro- four aryl ethylenes-triphenylimidazolyls
In the twoport flask of 25ml, by 4,4 '-two chloro- (neighbour) two benzaldehydes (0.46g, 1mmol), 4,4 '-dimethoxies
Base-benzil (1.08g, 4mmol) and ammonium acetate (3.08g, 40mmol) are dissolved in acetic acid (10ml).Reactant is being heated to
Under the conditions of 90 DEG C, it is stirred to react one day.After to the end of reacting, reaction solution is added dropwise in saturated salt solution dropwise, filtering is received
Collect white precipitate, washes, it is dry.Then residue is purified on silica gel column chromatography, obtains pale yellow powder 0.65g, yield
67.7%.
4) synthesis of 4,4 '-two chloro- thioxanthones loop coil bisglyoxaline molecules
In the twoport round-bottomed flask (100ml) equipped with constant pressure funnel, 4,4 '-two chloro- four aryl ethylenes-are added
Triphenylimidazolyl (0.4g, 0.42mmol) is then dissolved in 40ml methylene chloride.By iron blood salt (2.07g, 6.3mmol) and hydrogen
Potassium oxide (0.71g, 12.6mmol) is dissolved in 40ml deionized water, then in careful addition constant pressure funnel.Double
Masking foil shading is covered on mouth round-bottomed flask, iron blood saline solution is added dropwise dropwise, is vigorously stirred at room temperature 12 hours.Fully reacting
Later, upper strata aqueous phase is extracted with dichloromethane, merges organic phase, it is dry, it is spin-dried for solvent.Then by residue on silica gel is layer-by-layer
It purifies and obtains target product, 0.37g, 93%, i.e., it is reacted according to following general formula.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of loop coil bisglyoxaline molecule, which is characterized in that the loop coil bisglyoxaline molecule has such as formula (one) or formula (two) institute
The molecular structural formula shown
Wherein, X O, S, SO2Or Se；R1For H, F, Cl, Br, I, N (CH3)2Or O (CH2)nCH3；R2For H, F, Cl, N (CH3)2Or
O(CH2)nCH3, n be 0~7 integer.
2. loop coil bisglyoxaline molecule as described in claim 1, which is characterized in that the X is S or O, R1For H or OCH3, R2For
H,OCH3, F or Cl.
3. loop coil bisglyoxaline molecule as described in claim 1, which is characterized in that its phosphorescence fluorescent lifetime when temperature is 77K
Up to 1.6 seconds.
4. a kind of preparation method of the loop coil bisglyoxaline molecule as described in claims 1 to 3 any one, which is characterized in that with
Benzophenone is raw material, its corresponding dibromo aromatic ring olefin product is prepared by Corey-Fuchs reaction；Then with it is o-
Suzuki reaction occurs for formaldehyde phenyl boric acid, obtains replacing four aryl ethylenes together with position-ortho position aldehyde radical；Again with benzil in acetic acid, second
Leuckart occurs in sour ammonium to react to obtain together with position-ortho position tetraphenylethylene-triphenylimidazolyl；Finally in K3Fe(CN)6/ KOH's
Under oxidation, the loop coil bisglyoxaline molecule is obtained by free radical cycloaddition.
5. the preparation method of loop coil bisglyoxaline molecule as claimed in claim 4, which comprises the steps of:
(1) diphenylmethanone and carbon tetrabromide, triphenylphosphine are dissolved in toluene according to molar ratio 1:2~4:4~8, are heated
It flows back 1~4 day to 100~140 DEG C, after fully reacting, is spin-dried for solvent, residue is separated using silica gel column chromatography, then
The product being collected into is obtained into 1,1 '-two bromo- 2,2 '-diphenylethlenes with ethyl alcohol recrystallization；
(2) 1,1 '-the two bromo- 2,2 '-diphenylethlenes for obtaining step (1) and adjacent benzaldehyde phenyl boric acid, potassium carbonate and zero
Valence palladium catalyst is dissolved in the mixed solution of toluene and water according to molar ratio 1:2~4:4~8:0.05~0.1,90~110
It under the conditions of DEG C, is reacted 12~24 hours under nitrogen atmosphere, after fully reacting, water phase is extracted with dichloromethane, merges organic phase,
Then it is spin-dried for solvent, obtained residue is isolated and purified on silica gel column chromatography and obtains-two benzaldehyde of 2,2 '-diphenyl；
(3)-two benzaldehyde of 2,2 '-diphenyl that step (2) is prepared and benzil, ammonium acetate according to molar ratio 1:2~
4:10~30 are dissolved in acetic acid, are heated to 70~100 DEG C, are stirred to react 24~48 hours, to the end of reacting after, will react
Liquid is added dropwise in saturated salt solution dropwise, and white precipitate is collected by filtration, and is washed, dry, then by residue in silica gel column chromatography
Upper purifying obtains-two triphenylimidazolyl of 2,2 '-diphenyl；
(4) iron blood salt and potassium hydroxide are dissolved in deionized water, are added dropwise to 2, the 2 '-diphenyl-that step (3) is prepared
In two triphenylimidazolyls, described 2 ,-two triphenylimidazolyl of 2 '-diphenyl is dissolved in methylene chloride, the iron blood salt, hydroxide
Potassium and 2, the molar ratio of-two triphenylimidazolyl of 2 '-diphenyl are 10~20:20~50:1, at room temperature stirring 2~12 hours, instead
After answering completely, upper strata aqueous phase is extracted with dichloromethane, merges organic phase, it is dry, it is spin-dried for solvent, then by residue in silica gel
Purifying obtains the loop coil bisglyoxaline molecule on column chromatography.
6. a kind of application of the loop coil bisglyoxaline molecule as described in claims 1 to 3 any one, which is characterized in that be applied to
Prepare phosphorescent light-emitting materials.
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| WO2015090504A2 (en) * | 2013-12-19 | 2015-06-25 | Merck Patent Gmbh | Heterocyclic spiro compounds |
| CN106478645A (en) * | 2016-09-21 | 2017-03-08 | 陕西科技大学 | A kind of fragrant cyclosubstituted spiro indole diketopiperazine compound and its synthetic method |
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| WO2015090504A2 (en) * | 2013-12-19 | 2015-06-25 | Merck Patent Gmbh | Heterocyclic spiro compounds |
| CN106478645A (en) * | 2016-09-21 | 2017-03-08 | 陕西科技大学 | A kind of fragrant cyclosubstituted spiro indole diketopiperazine compound and its synthetic method |
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